Levocetirizine-Loaded Electrospun Fibers from Water-Soluble Polymers: Encapsulation and Drug Release.

Electrospun fibers containing levocetirizine, a BCS III drug, were prepared from three water-soluble polymers, hydroxypropyl methylcellulose (HPMC), polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA). Fiber-spinning technology was optimized for each polymer separately. The polymers contained 10 wt% of the active component. An amorphous drug was homogeneously distributed within the fibers. The solubility of the drug in the polymers used was limited, with a maximum of 2.0 wt%, but it was very large in most of the solvents used for fiber spinning and in the dissolution media. The thickness of the fibers was uniform and the presence of the drug basically did not influence it at all. The fiber diameters were in the same range, although somewhat thinner fibers could be prepared from PVA than from the other two polymers. The results showed that the drug was amorphous in the fibers. Most of the drug was located within the fibers, probably as a separate phase; the encapsulation efficiency proved to be 80-90%. The kinetics of the drug release were evaluated quantitatively by the Noyes-Whitney model. The released drug was approximately the same for all the polymers under all conditions (pH), and it changed somewhere between 80 and 100%. The release rate depended both on the type of polymer and pH and varied between 0.1 and 0.9 min-1. Consequently, the selection of the carrier polymer allowed for the adjustment of the release rate according to the requirements, thus justifying the use of electrospun fibers as carrier materials for levocetirizine.

Preparation and Characterization of Fibrous Alumina and Zirconia Toughened Alumina Ceramics with Gradient Porosity.

This paper investigated a synthesis process for highly porous Al2O3, Y-ZTA, and Ce-ZTA ceramic nanocomposites with gradient microstructure and improved mechanical properties. Ceramic nanofibres were synthesized as the starting material. The gradient microstructure was developed during spark plasma sintering using an asymmetric graphite arrangement that generated significant temperature differences (80-100 °C) between the opposite sides of the samples. Structural and mechanical properties of the fibrous ceramic composites were investigated. The effect of the temperature gradient on properties was also discussed. While the asymmetric configuration resulted in a gradient porosity, reference samples fabricated in standard graphite configuration were uniformly porous. The gradient structure and the ZrO2 addition led to improved hardness and compression strength of the sintered samples. However, the opposite sides of the samples exhibited considerable variations in both microstructure and in terms of properties. The upper part of the Ce-ZTA ceramic showed a highly porous structure with 18.2 GPa hardness, while the opposite side was highly densified with 23.0 GPa hardness. Compressive strength was 46.1 MPa and 52.1 MPa for Y-ZTA and Ce-ZTA sintered at 1300 °C, respectively, despite their high porosity. The research provided a promising approach to prepare highly porous ZTA composites with high strength for a wide range of applications.

Preparation of Biocomposites with Natural Reinforcements: The Effect of Native Starch and Sugarcane Bagasse Fibers.

Biocomposites were prepared from poly(lactic acid) and two natural reinforcements, a native starch and sugarcane bagasse fibers. The strength of interfacial adhesion was estimated by model calculations, and local deformation processes were followed by acoustic emission testing. The results showed that the two additives influence properties differently. The strength of interfacial adhesion and thus the extent of reinforcement are similar because of similarities in chemical structure, the large number of OH groups in both reinforcements. Relatively strong interfacial adhesion develops between the components, which renders coupling inefficient. Dissimilar particle characteristics influence local deformation processes considerably. The smaller particle size of starch results in larger debonding stress and thus larger composite strength. The fracture of the bagasse fibers leads to larger energy consumption and to increased impact resistance. Although the environmental benefit of the prepared biocomposites is similar, the overall performance of the bagasse fiber reinforced PLA composites is better than that offered by the PLA/starch composites.

Deformation and Failure Mechanism of Particulate Filled and Short Fiber Reinforced Thermoplastics: Detection and Analysis by Acoustic Emission Testing.

Acoustic emission, the detection of signals during deformation, is a frequently used method for the study of local deformation processes occurring in heterogeneous polymer systems. Most of these processes result in the evolution of elastic waves which can be detected by appropriate sensors. The analysis of several parameters characterizing the waves offers valuable information about the possible deformation mechanism. The acoustic emission testing of composites may yield very different number of signals from a few hundred to more than 100,000. This latter was proved to be affected mainly by particle size, interfacial adhesion and composition, but other factors, such as matrix modulus and specimen size, also influence it. Local deformation processes are claimed to have a strong effect on macroscopic properties. Indeed, a close correlation was found between the initiation stress of the dominating particle related process derived from acoustic emission testing and the tensile strength in both polypropylene (PP) and poly(lactic acid) (PLA) composites. However, in polyamide (PA)-based heterogeneous polymer systems, deformations related to the matrix dominated composite properties. Besides forecasting failure, the method makes possible the determination of the inherent strength of lignocellulosic fibers being around 40 MPa as well as the quantitative estimation of adhesion strength for composites in which interactions are created by mechanisms other than secondary forces. The proposed approach based on acoustic emission testing proved that in PP/CaCO3 composites, the strength of adhesion can be increased by ten times from about 100 mJ/m2 to almost 1000 mJ/m2 in the presence of a functionalized polymer.

Poly-ε-Caprolactone/Halloysite Nanotube Composites for Resorbable Scaffolds: Effect of Processing Technology on Homogeneity and Electrospinning.

Polycaprolactone (PCL)/halloysite composites were prepared to compare the effect of homogenization technology on the structure and properties of the composites. Halloysite content changed from 0 to 10 vol% in six steps and homogeneity was characterized by various direct and indirect methods. The results showed that the extent of aggregation depends on technology and on halloysite content; the size and number of aggregates increase with increasing halloysite content. Melt mixing results in more homogeneous composites than the simple compression of the component powders or homogenization in solution and film casting. Homogeneity and the extent of aggregation determines all properties, including functionality. The mechanical properties of the polymer deteriorate with increasing aggregation; even stiffness depends on homogeneity. Strength and deformability decreases drastically as the number and size of aggregates increase. Not only dispersed structure, but also the physical state and crystalline structure of the polymer influence homogeneity and properties. The presence of the filler affects the preparation of electrospun fiber scaffolds as well. A part of the filler is excluded from the fibers while another part forms aggregates that complicates fiber spinning and deteriorates properties. The results indicate that spinning is easier and the quality of the fibers is better if a material homogenized previously by melt mixing is used for the production of the fibers.

The Role of Interfacial Adhesion in Polymer Composites Engineered from Lignocellulosic Agricultural Waste.

This paper presents a comprehensive study about the application of a lignocellulosic agricultural waste, sunflower husk in different polymer composites. Two types of milled sunflower husk with different geometrical factors were incorporated into polypropylene, low-density and high-density polyethylene, polystyrene (PS), glycol-modified polyethylene terephthalate (PETG) and polylactic acid (PLA). The filler content of the composites varied between 0 and 60 vol%. The components were homogenized in an internal mixer and plates were compression molded for testing. The Lewis-Nielsen model was fitted to the moduli of each composite series, and it was found that the physical contact of the filler particles is a limiting factor of composite modulus. Interfacial interactions were estimated from two independent approaches. Firstly, the extent of reinforcement was determined from the composition dependence of tensile strength. Secondly, the reversible work of adhesion was calculated from the surface energies of the components. As only weak van der Waals interactions develop in the interphase of polyolefins and sunflower husk particles, adhesion is weak in their composites resulting in poor reinforcement. Interfacial adhesion enhanced by specific interactions in the interphase, such as π electron interactions for PS, hydrogen bonds for PLA, and both for PETG based composites.

Improved Release of a Drug with Poor Water Solubility by Using Electrospun Water-Soluble Polymers as Carriers.

In an attempt to improve the solubility of valsartan, a BCS II drug, fibers containing the drug were prepared from three water-soluble polymers, hydroxypropyl-methyl-cellulose (HPMC), polyvinyl-pyrrolidone (PVP), and polyvinyl-alcohol (PVA). Fiber spinning technology was optimized for each polymer separately. The polymers contained 20 wt% of the active component. The drug was homogenously distributed within the fibers in the amorphous form. The presence of the drug interfered with the spinning process only slightly, the diameters of the fibers were in the same range as without the drug for the HPMC and the PVA fibers, while it doubled in PVP. The incorporation of the drug into the fibers increased its solubility in all cases compared to that of the neat drug. The solubility of the drug itself depends very much on pH and this sensitivity remained the same in the HPMC and PVP fibers; the release of the drug is dominated by the dissolution behavior of valsartan itself. On the other hand, solubility and the rate of release were practically independent of pH in the PVA fibers. The different behavior is explained by the rate of the dissolution of the respective polymer, which is larger for HPMC and PVP, and smaller for PVA than the dissolution rate of the drug. The larger extent of release compared to neat valsartan can be explained by the lack of crystallinity of the drug, its better dispersion, and the larger surface area of the fibers. Considering all facts, the preparation of electrospun devices from valsartan and water-soluble polymers is beneficial, and the use of PVA is more advantageous than that of the other two polymers.

Improving physical properties and retrogradation of thermoplastic starch by incorporating agar.

To develop functional and sustainable packaging materials from starch and to enhance their properties, agar was added to thermoplastic corn starch (TPS) in a wide concentration range and the products were prepared either by casting or melt blending with a high glycerol content. The role of agar in the mechanical and barrier performance of films, as well as the compatibility of TPS and agar was systematically evaluated. In addition, the retrogradiation of starch in various blends after long storage periods was widely characterized. Results proved that the addition of agar to TPS resulted in films with promising barrier and tensile properties. Stiffness and strength increased considerably by increasing agar content, while deformability of blends was better than those of pure TPS. Agar incorporation decreased water permeability and solubility and improved light transmittance. Retrogradation of the dry blends was significantly smaller than that of pure TPS owing to the strong starch/agar interaction.

Thermoplastic starch/wood composites: interfacial interactions and functional properties.

Thermoplastic starch (TPS)/wood composites were prepared from starch plasticized with 36 wt% glycerol. The components were homogenized by dry-blending, extruded and injection molded to tensile bars. Tensile properties, structure, deformation, water adsorption and shrinkage were determined as a function of wood content, which changed between 0 and 40 vol% in 7 steps. The modification of TPS with wood particles improves several properties considerably. Stiffness and strength increases, and the effect is stronger for fibers with larger aspect ratio. Wood fibers reinforce TPS considerably due to poor matrix properties and strong interfacial interactions, the latter resulting in the decreased mobility of starch molecules and in the fracture of large wood particles during deformation. Strong interfacial adhesion leads to smaller water absorption than predicted from additivity, but water uptake remains relatively large even in the presence of wood particles. The shrinkage of injection molded TPS parts is very large, around 10%, and dimensional changes occur on a very long timescale of several hundred hours. Shrinkage decreases to a low level already at 15-20 vol% wood content rendering the composites good dimensional stability.

Adhesion and micromechanical deformation processes in PLA/CaSO4 composites.

PLA/CaSO4 composites were prepared from uncoated and stearic acid coated filler particles in a wide composition range. The strength of interfacial adhesion was estimated quantitatively with three independent methods. Structure was characterized by DSC, XRD and SEM measurements, while mechanical properties by tensile and instrumented impact tests. The results proved that adhesion is twice as strong in composites prepared with the uncoated particles than in those containing the coated filler. Coating changes also local deformation processes around the particles. Although debonding is the dominating micromechanical deformation process in all composites, local plastic deformation is larger around coated particles. The extent of this deformation depends very much also on the local distribution of particles. The final properties and performance of the composites depend unambiguously on the micromechanical deformation processes occurring during loading, on debonding and the subsequent plastic deformation. Stearic acid used for the coating of the filler seems to dissolve in the polymer and locally change its properties.

Determination of the surface characteristics of particulate fillers by inverse gas chromatography at infinite dilution: a critical approach.

CaCO3 fillers were investigated by inverse gas chromatography (IGC) to determine the dispersion component of their surface tension as well as their acid-base character. Because of the high energy of the filler surface, it readily adsorbs water, thus the parameters measured by IGC depend on the conditioning temperature, as well as on the measurement conditions. As a consequence, the determined surface characteristics are not material constants; different fillers or the effect of coating can be compared only under standard conditions. The use of the same conditioning and measurement temperature eliminates the effect of measurement time. Under appropriate standard conditions the acid-base characteristics of the filler can be determined reliably. However, the accuracy of the determination and the value of the derived parameters depend very much on the selected approach and on the acid-base constants used for the probe molecules. A critical analysis of the approaches used in the current literature pointed out those that yield the most reasonable and accurate values. The results prove that the surface of CaCO3 is strongly basic in character. Coating significantly reduces basicity. Surprisingly, the filler coated with an amount of stearic acid resulting in minimum surface tension showed relatively strong acidity, which indicates a coating exceeding monolayer coverage and/or the uneven distribution of the surfactant on the surface.